Phenyl carbamates

ABSTRACT

O-PHENYLCARBAMATES, E.G. THOSE OF THE FORMULA   (R1-N(-R2)-COO-),(R4-O-CH(-X3-R3)-),X1,X2-BENZENE   R1=H, ALKYL OR ALKENYL R2=ALKYL OR ALKENYL R3,4=ALKYL, ALKENYL, ALKYNYL R3+R4=ALKYLENE OR ALKENYLENE X1,2=H, ALIPHATIC RADICAL, HALOGEN OR NITRO X3=O OR S   ARE BOCIDES, E.G. INSECTICIDES.

United States Patent Ofice Patented Dec. 25, 1973 ABSTRACT OF THE DISCLOSURE O-phenylcarbamates, e.g. those of the formula R =H, alkyl or alkenyl Ry: alkyl or alkenyl R =alkyl, alkenyl, alkynyl R +R =alkylene or alkenylene X =H, aliphatic radical, halogen or nitro X =O or S are biocides, e.g. insecticides.

CROSS REFERENCES TO RELATED APPLICATIONS This is a continuation of application Ser. No. 2,445, filed Jan. 12, 1970, now abandoned. Said application was a continuation-in-part of application Ser. No. 728,835, filed May 13, 1968, which in turn was a division of application Ser. No. 493,256, filed Oct. 5, 1965, both now abandoned.

SUMMARY OF THE INVENTION The present invention concerns and has for its object the provision of new O-phenyl-carbamates of Formula I Xa-Ra in which each of R and R is hydrogen, lower alkyl or lower alkenyl, each of X and X is hydrogen, a saturated or unsaturated lower aliphatic radical, halogeno or nitro, X is oxygen or sulfur and each of R and R are alkyl, alkenyl or alkynyl or, when taken together, represent alkylene or alkenylene forming with the remaining moiety a 5 to 7 membered heterocycle, and in which R and R are unsubstituted or substituted by lower aliphatic radicals, halogeno, nitro or free or etherified hydroxy or mercapto, as well as of corresponding pesticidal preparations and methods for the preparation and application of these products. Said preparations are useful in the control of a wide variety of vegetable and animal pests.

DESCRIPTION OF THE PREFERRED EMBODIMENT The radicals R and R are identical or different and represent, for example, hydrogen, methyl, ethyl nor i-propyl or allyl.

The moiety s-Rs \0R4 in 0- or m-position results from reacting the corresponding aldehyde, semiacetal or semimercaptal, for example, with methanol, ethanol, propanol, isopropanol, allyl alcohol, propargyl alcohol, Z-methoxyethanol, Z-methylmercaptoethanol, 2-chlorethanol, 2-bromethanol or Z-hydroxyethanethiol, or the corresponding semiacetal with methylmercaptan, ethylmercaptan, n-propylmercaptan, isopropylmercaptan, n-butylmercaptan, allylmercaptan, chlorallylmercaptan, dichlorallylmercaptan, propargylmercaptan, 2- methoxyethanethiol, or 2-methylmercaptoethanethiol. In case R and R when taken together, represent alkylene or alkenylene, said moiety results from the reaction of the corresponding aldehyde, for example, with racemic 1,2-propanediol,

(+) (S 1,2-propanediol,

( (R) 1,2-propanediol, 3-fluoro-1,2-propanediol, 3-chloro-1,2-propanediol, 3-brom0-1,2-propanediol, 3-iodo-1,2-propanediol, B-methoxy-1,2-propanediol, 3-ethoxy-1,2-propanediol, 3-isopropoxy-1,Z-propanediol, 3-allyloxy-1,2-propanediol, 3-methallyl0xy-1,2-propanediol, 3-propargyloxy-1,2-propanediol, 3-acetoxy-1,2-propanediol, 3-methylmercapto-1,2-propanediol, 3-chlorallylmercapto-1,2-propanediol, glycerol,

1,3-propanediol,

2-chloro-l ,3-propanediol, 2-bromo-1,3-propanediol, Z-nitro- 1,3-propanediol,

(+) (R) 1,2-butanediol,

() (S 1,2-butanediol,

racemic 1,2-butanediol, 1,3-butanediol,

1,4-butanediol, meso-2,3-butanediol,

() (2R 3R) -2,3-butanediol, (2S 3S) -2,3-butanediol, 1-butene-3,4-diol, 2-butene-1,4-diol, 2-hydroxymethyl-2-propenl-ol, 2-hydroxymethyl-2-buten-l-ol, Z-methyl- 1,2-propanediol, 3-chloro-2-methyl-1,2-propanediol, 3-chloro-2-chloromethyl-1,2-propanediol, 2-methyl-1,3-propanediol, 2-nitro-2-methyl-1,3-propanediol, 1,2-pentanediol,

1,3-pentanediol,

2,3-pentanediol,

2,4-pentanediol, 1-pentene-3,4-dio1, 2n1ethyl-1,2-butanediol, 2-methyl-1,3-butanediol, 2-methyl-2,3-butanediol, 2-methyl-2,4-butanediol, 2-methyl-3,4-butanedio1,

3 2-ethyl-1,3-propanediol, 1,4-dichloro-2-methyl-2,3-butanediol, 4-bromo-2-methyl-2,3-butanediol, 4-iodo-2-methyl-2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 2,2-bischloromethyl-1,3-propanediol, 2,4-hexanediol, 2-methyl-2,3 -pentanediol, 3-methyl-2,4-pentanediol, 2,2-dimethyl-3 ,4-butanediol, 1,5-hexadiene-3,4-diol, 2-ethanol-1-thiol, 2-propanol-l-thiol, 3-chloro-2-propanoll-thiol, 3-propanoll-thiol.

Accordingly, each of R and R is preferably lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy-lower alkyl, lower alkylmercapto-lower alkyl, halo-lower alkyl, hydroxy-lower alkyl, halo-lower alkenyl, or R and R when taken together, preferably lower alkylene, monoor dihalo-lower alkylene, lower alkoxy-lower alkylene, lower alkenyloxy-lower alkylene, lower alkynyloxy-lower alkylene, lower alkanoyloxy-lower alkylene, lower alkylmercapto-lower alkylene, halo-lower alkenylmercapto-lower alkylene, hydroxy-lower alkylene, nitro-lower alkylene, lower alkenylene, hydroxy-lower alkenylene or lower alkadienylene. The term lower referred to above and hereinafter in connection with organic radicals or compounds respectively, defines such with up to 6 carbon atoms.

The radicals X and X are identical or different and represent, for example, hydrogen, lower alkyl, e.g. methyl, lower alkoxy, alkenyloxy or alkynyloxy or -mercapto or haloalkenylmercapto, e.g. methoxy, isopropoxy, allyloxy, propargyloxy, methylmercapto, allylmercapto or chlorallylmercapto, halogeno, e.g. fluoro, chloro, bromo or iodo, trifiuoromethyl, nitro, di-lower alkylamino or di-lower alkenylamino. In this series most preferred compounds are obtained when X and X each represents a hydrogen atom, a lower alkyl or a lower alkoxy radical. Accordingly, the above mentioned aldehydes, represent, for example,

salicylaldehyde,

4-methyl salicylaldehyde, S-methyl-salicylaldehyde, 4-methoxy-salicylaldehyde, 4-isopropoxy-salicylaldehyde, 4-chloro-salicylaldehyde, 5-chloro-salicylaldehyde, S-bromo-salicylaldehyde, S-methylmercapto-salicylaldehyde, 4 trifluoromethyl-salicylaldehyde, 5-nitro-salicylaldehyde, 4-dimethylamino-salicylaldehyde, 3,5-dichloro-salicylaldehyde,

3 ,5 -dinitro-salicylaldehyde, 3-hydroxybenzaldehyde, 2-chloro-3-hydroxybenzaldehyde, 6-bromo-3-hydroxybenzaldehyde, or 5-hydroxy-3-methylbenzaldehyde.

The compounds of the invention exhibit valuable properties, for example, biocidal, especially insecticidal and acaricidal properties. Furthermore, they act also as herbicides, bactericides, fungicides and molluscicides. Inter alia, these carbamates develop a very strong action, for example, against housefiies, aphids, caterpillars and beetles, for example, corn weevil and Colorado beetle. Their contact effect is far superior to that of the known active substance carbaryl (N-methyl-a-naphthylcarbamate).

They are not only suitable for use as herbicides, but When applied in a concentration that does not produce phytotoxic effects, they may also be used in plant protection since they develop an excellent effect against harmful microorganisms, for example against fungi, for example Alternarz'a solani, Phytophthora infestans and Septoria apii, as well as against harmful insects, acarids, nematodes and their ova and larvae. They may also be used quite generally as microbicides, for example, against Aspergillus species.

Particularly useful are compounds of Formula I in which each of R and R is hydrogen, lower alkyl or lower alkenyl, each of X and X is hydrogen, lower alkyl, lower alkoxy, lower alkenyloxy, lower alkynyloxy, lower alkylmercapto, lower alkenylmercapto, lower alkynylmercapto, lower haloalkenylmercapto, halogeno, trifluoromethyl, nitro, di-lower alkylamino or di-lower alkenylamino, X is oxygen or sulfur and each of R and R is lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy-lower alkyl, lower alkylmercapto-lower alkyl, halolower alkyl, hydroxy-lower alkyl, halo-lower alkenyl or R and R when taken together, represent lower alkylene, monoor di-halo-lower alkylene, lower alkoxy-lower alkylene, lower alkenyloxy-lower alkylene, lower alkynyloxy-lower alkylene, lower alkanoyloxy-lower alkylene, lower alkylmercapto-lower alkylene, halo-lower alkenylmercapto-lower alkylene, hydroxy-lower alkylene, nitrolower alkylene, lower alkenylene, hydroxy-lower alkenylene or lower alkadienylene, forming with the remaining moiety a 5 to 7 membered heterocycle.

Especially suitable for insect control are the carbamates of Formula I wherein R is hydrogen, R is lower alkyl, each of X and X is hydrogen, methyl, chloro, bromo, trifluoromethyl or nitro, X is oxygen or sulfur and each of R and R is lower alkyl, lower alkenyl or lower alkynyl or R and R when taken together represent alkylene or alkenylene with 2 to 4 carbon atoms, forming with the remaining moiety a 5 to 7 membered heterocycle and being unsubstituted or substituted by halogen, nitro, hydroxy, lower alkoxy or lower alkenyloxy.

Preferred are compounds of Formulae II and III Xa-Ra and X3 R3 0-- R (II) in which X is oxygen or sulfur and each of R and R is lower alkyl, lower alkenyl or lower alkynyl or R and R when taken together, represent alkylene or alkenylene with 2 to 4 carbon atoms, forming with the remaining moiety a 5 to 7 membered heterocycle and being unsubstituted or substituted by halogen, nitro, hydroxy, lower alkoxy or lower alkenyloxy.

Most preferred are compounds of the Formula II in which X is oxygen or sulfur and each of R and R is lower alkyl or R and R when taken together, represent alkylene or alkenylene with 2 to 4 carbon atoms, forming with the remaining moiety a 5 to 7 membered unsubstituted heterocycle and of Formula IV in which X is oxygen or sulfur and each of R and R is hydrogen or lower alkyl.

Outstanding are the compounds of Formula IV, in which X is oxygen or sulfur and each of R and R is hydrogen or methyl.

The compounds of the invention are prepared, for example, by reacting a phenol of the Formula V X3R3 x, o{1\ O-Rl X1 (V) with a reactive derivative of carbonic acid and with The reaction of the phenol with the reactive derivative of carbonic acid and the amine may be carried out in either sequence, depending to some extent on the constitution of the required final product. Accordingly, said phenol or an alkali metal salt thereof may be reacted, for example, with phosgene and the resulting chlorocarbonate or carbonate condensed with R -NH-R Alternatively, said amine may be first reacted with phosgene and the resulting carbamic acid chloride or (when R or R represents hydrogen) the isocyanate readily formed from it, may be reacted with the phenol. Furthermore, a urethane derived from the amine, preferably an alkyl urethane, may be reacted with the phenol (transesterification). It is also possible to react a urea derived from the amine with the phenol preferably at a raised temperature.

The products so obtained are open-chain or cyclic acetals or mercaptals, depending on the stoichiometric proportions of the starting materials and on the valency of the alcohols or mercaptans. According to the size of the ring and the kind of hetero atom present in the acetalized moiety, the carbamates of this invention may be designated as derivatives of 1,3-dioxolan (from 1,2- glycols), of 1,3-dioxan (from 1,3-glycols), of 1,3-dioxepan (from 1,4-glycols) or of 1,3-oxathi0lans (from 1,2- hydroxymercaptans) The starting materials used are known or, if new, can be prepared analogous to the method for the known products (cf. for example Houben-Weyl, Methoden der Organischen Chemie, vol. 7, part 1, Stuttgart, 1945). For example, the phenols of Formula V are prepared by reacting an orthoor meta-hydroxy-benzaldehyde with a lower alcohol or mercaptan in the presence of an acid catalyst, for example zinc chloride, a mineral acid or paratoluenesulphonic acid. These reactions may also be carried outwith aldehyde derivatives, for example oximes, aldehydanils or acetals (transacetalization). Another suitable route is the acetalization with the aid of ortho-formic acid esters, formimine ethers, dimethylsulphite or orthosilicic acid esters in the presence of lower aliphatic alcohols. Another route leading to said phenols is the reaction of suitable halides with alkali metal or alkaline earth metal alcoholates.

Said acetalization may be performed in two stages, with the semiacetals or semimercaptals being formed in the first reaction stage. When different alcohols are used in the two reaction stages, mixed acetals, i.e. monothioacetals, are obtained.

When optically active alcohols or mercaptans are used, there may be prepared optically active phenols of the Formula V and from them opticaly active carbamates of the Formula I. If its acetal moiety is cyclic and substituted, further isomerizing possibilities oifer themselves. A carbamate of the Formula I whose acetal residue is monosubstituted may be obtained in the cis-form or transform. In general, the present process for the manufacture of said carbamates given rise to mixtures of all possible isomers; these mixtures can 'be separated into their constituents by known methods, for example by crystallization. For the manufacture of the preparations of this invention to be used for pest control, however, the stereoisomer mixtures obtained in the manufacture of the active substances are generally used.

As mentioned in the beginning the present invention also provides pesticidal preparations comprising as the active ingredient at least one carbamate of the Formula I and, if desired, one of the following additives. Such additives are those commonly used in pesticidal preparations such as vehicles, solvents, diluents, dispersants, Wetting agents, adhesives, fertilizers and, if required, further pesticides. Corresponding spray solutions are prepared, for example, with petroleum fractions having a high to medium boiling range, for example diesel oil or kerosene, coal tar oil, or oils of vegetable or animal origin, as well as hydrocarbons, for example alkylated naphthalenes, tetrahydronaphthalene, if desired or required with the use of xylene mixtures, cyclohexanols, ketones or chlorinated hydrocarbons for example trichloroethane or tetrachloroethane, trichloroethylene or trior tetra'chlorobenzenes. It is advantageous to use organic solvents having a boiling point above C.

It is especially advantageous to prepare aqueous forms of application from emulsion concentrates, pastes or wettable spray powders by addition of water. Suitable emulsifiers or dispersants are non-ionic products, for example condensation products of aliphatic alcohols, amines or carboxylic acids with a long-chain hydrocarbon residue of about 10 to 20 carbon atoms with ethylene oxide, for example the "condensation product from octadecyl alcohol with 25 to 30 mols of ethylene oxide, or of commercial oleylamine with 15 mols of ethylene oxide, or of dodecylmercaptan with 12 mols of ethylene oxide. As suitable anionic emulsifiers, there may be mentioned the following: The sodium salt of dodecylbenzosulphonic acid, the potassium of triethanolamine salt of oleic acid or of abietic acid or of a mixture of these two acids, or the sodium salt of a petroleumsulphonic acid. Suitable cationic dispersants are quaternary ammonium compounds, for example cetyl pyridinium bromide and dihydroxyethyl benzyl dodecyl ammonium chloride.

For the manufacture of dusting and casting preparations, there may be used as solid vehicles: talcum, kaolin, bentonite, calcium carbonate, calcium phosphate or coal, cork meal, wood meal or other materials of vegetable origin. It is also very advantageous to manufacture the preparations in the form of granulates. The various forms of application may contain the conventional additives that improve the distribution, the adhesion, stability to rain or the penetration; as such substances there may be mentioned fatty acids, resin, glue, casein and alginates.

The preparations of this invention may be used by themselves or in conjunction or admixture with conventional pesticides, especially insecticides, acaricides, nematocides, bactericides, fungicides, herbicides and the like.

The following examples are intended to illustrate the invention and are not to be construed as being limitations thereon. Temperatures are given in degrees centigrade, and all parts or percentages wherever given are such by weight.

EXAMPLE 1 (a) Ortho( 1,3 -dioxolan-2-yl) -phenol A mixture of 244 parts of salicylaldehyde, parts of ethyleneglycol, 1 part of zinc chloride, 1 part by volume of concentrated phosphoric acid and 500' parts by volume of benzene was boiled in a circulating distillation apparatus until water was no longer being eliminated. The solution of the product was filtered and evaporated. The residue was distilled under a high vacuum. The product boiled at 88 to 91 C. under 0.04 mm. Hg pressure and melted at 67 to 70 C.

(b) Ortho- 1,3-dioxolan-2-yl) -phenyl- N-methyl-carbamate A solution of 50 parts of ortho-(l,3-dioxolan-2-yl)- phenol in 300 parts by volume of dry toluene was mixed with about 0.2 part by volume of triethylamine, and 20 parts of methylisocyanate were dropped into this solution at room temperature. The temperature rose gradually to 31 C. The mixture was kept for 1 day at room temperature. The product was filtered oil and crystallized from toluene; it melted at 111 to 114 C.

EXAMPLE 2 then dropwise with 122 parts of salicylaldehyde; the temperature of the mixture rose. The reaction mixture was stirred for 1 hour at room temperature, then diluted with 500 parts by volume of ether and washed with sodium bicarbonate solution and then with water until the wash- When glycols (polyols) were reacted with unsubsti- 5 tuted or substituted orthoor meta-hydroxybenzaldehydes, lngs ran neutral. The solution was dried over anhydrous the condensation as described 1n Example 1 led to cy- SOdwm sulphate, filtered and evaporated.

chc acetals. When these acetals were reacted with meth- The VISCOUS residue was heated under a high vacuum ylisocyanate, they furnlshed, for example, the following at a bath temperature of 160 C., and the volatile phase carbamates: 10 was condensed. The condensate was then fractionated.

N0. Aldehyde Glycol Cyclic acetal Carbamate 1 salicylaldehyde 1,2-propanediol B.P. 85 C./0.03 mm. rtho-(4-methyl-1,3-dioxolan-2-yl)-phenyl-N-methyl-carbamate Hg. (crystallizes gradually). 2 do 2,3-butanedio1 (com- B.P. 86 C./0.07 mm. Ortho-(4,5-dimethyl-1,3dioxolan-2-yl)-phenyl-N-methyl-carbamercial mixture of Hg. mate, M.P. 70105 O. stereoisomers). 3 do 1-butene-3,4-di0l B 1;- 82 C-/0.08 mm. Ortho-(4-vinyl-1,3dioxolan-2-y1)-phenyl-N-methyl-carbamate.

g. 4 .-do G1ycero1- -monoehloro- B.P. 111-114 C./0.3 Orth0-(4-chlor0methyl-l,3-dioxolan-2-yl)-phenyl-N-methylhydrin. nun. g. carbamate, M.P. about 30 to 70 C. 5 do Glycerol M.P. 148 to 149 C. Ortho-(4-hydroxymethyl-1,3-dioxolan-2-yl)-phenyl-N-methyl- (from acetonitrile). carbamate, or ortho-(5 hydroxy-1,3-dioxan-2-yl) -phenyl'N- Inethyl-carbamate, M.P. 130 to 134 0. As by-product the corresponding bis-N-methyl-carbamate melting at 170 to 172 C. was obtained. 5 do 1,3-propanediol B.P. 92 to 96 0.10.01 Ortho-(1,3-dioxan-2-yl)-phenyl-N-methyl-carbamate, M.P.

mm. g. 125 to 127 C. (from toluene). 7 do 1,3-butanediol B.P. 89 to 95 C./0.06 Ortho-(4-rnethyl-l,3-dioxan-2-yl)-phenyl-N-rnethyl-carbamate,

mm. Hg. M.P. 146 to 148 C. (irom acetonitrile). g do Neopentylglycol B.P. 90 C./0.06 mm. Ortho-(5,5-dimethyl-1,3-dioxan-2-y1)-phenyl-N-methyl-carba- Hg, M.P. 58-00 C. mate. M.P. 122 to 124 C. (from carbon tetrachloride). 9 do 3-methyl-2,4-pentane B.P. 93 C./0.01 nun. Ortho-(4 5 6-trimethyl-1,3-dioxan-2-yl)-phenyl-N-methy[-carbae101. Hg. mate, M.P. 11s to 130 0.

10 do 2-mcthyl-2-nitr0-1,3 M.P. 90 to 93 C. (from Ortho-(5-methyl-5-nitro-1,3-dioxan-2-yl)-phenyl-N-methylpropanediol. ether cyclohexane). carbamate, M.P. 131-133 C. (from isopropanol).

11 do 2-butene-L4-diol B.P. 87 C./0.03 mm. Ortho-(1-3-dioxep-5-en-2-yl)-phenyl-N-methyl-carbamate, M.P.

Hg. 94-95 C. (from toluene).

12 4-methylsalicyl- Ethyleneglycol B.P. 98 C./0.02 rnm. Ortho-(1,3-dioxolan-2-yl)-meta-methylphenyl-N-methyl-carbaaldehyde. Hg; crystallizes. mate, M.P. 96 to 99 C. (from toluene).

13 5-methylsalicyldo B.P. 9596 C./0.0l mm. Ortho (1,3-dioxolan-2-yl)-para-methylphenyl-N-methyl-carbaaldehyde. Hg. mate, M.P. 104 to 106 C. (from carbon tetrachloride).

14 Mixture of 4- and 6- 1,2-propanediol B.P. 90 C./0.7 mm. Ortho-(4-methyl-1,3-dioxolan-2-yD-rnetaand meta-tritluorotrifluoromethyl- Hg. methylphenyl-N-methyl carbamate (viscous oil). salicylaldehyde. l

15. 5-chlorosalicylaldehyde Ethyleneglycol M.P. 82 C. (from Para-chloro-ortho-(l,3-d1oxolan-2-yl)-phenyl-N-methyl carbatoluene). mate, M.P. 100-112 C. (from benzene plus hexane).

16 Mixture 014- and 6- 1,2-propanedi0L- Orthn-(4-methyl-1,3dioxolan-2-yl)-metaand meta-ehlorochlorosalicylaldehyde. Hg phenyl-N-methyl carbarnate, M.P. about 90 to 100 C.

17--. S-bromosalieylaldehyda- EthyleneglycoL. M.P. 81 C. (from Para-bromo-ortho-(l,3 dioxolan-2-yl)-phenyl-N-methyl-carba- 116K mate, M.P. 107 to 109 C. (from ethylene chloride).

18-. 3,5-dibromo-salicy1- ..d0 Ortho-para-dibromo-ortho-(l,3 dioxolan-2-yl)-phenyl-N-methylaldehyde. Hg, M.P. 60 to 64 C. carbarnate, M.P. 135139 C. (from acetonitrile).

19 3,5-dinitro-salicylald0 M P. 134140 C. (from Ortho-para-dinitro-ortho-(1,3-dioxolan-2-y1)phenyLN-methyldehyde. chlorobenzene). car-bamate, M.P. 149l55 C. (from acetone).

20 Meta-hydroxybenzall0 BR 113 to 115 C./0.03 Meta-(1,3-dioxolan-2-yl)-phenyl-N-methyl-carbamate, M.P. 73

dehyde. mm. Hg. to 77 C. (from toluene).

21 do 2,3-b a d ol (OO 5 C./0.1 mm. Meta-(4,S-dimethyl-1,3-dioxolan-2-yl) phenyl-N-methyl-carbamercial). Hg. mate, viscous oil.

1 4(6)-tn'fluoromethyl-salieylaldehyde can be prepared from B-trifluoromethylphenol by the method of J. O. Dufi [.T. Chem. Soc. 1941, page 547, Free. Iowa Acad. Sci. 52, page 191 (1945)]. It boils at 77 to 80 C. under 14 mm. Hg pressure.

EXAMPLE 3 Salicylaldehyde diethyl acetal A mixture of 122 parts of salicylaldehyde, 180 parts of orthoformic acid ethyl ester and 120 parts of anhydrous ethanol was mixed with 1 ml. of concentrated hydrochloric acid, whereupon the whole heated up spontaneously. After a short time, the solution was heated to the boil and then evaporated under vacuum, and the residue distilled under a high vacuum. The product passed over at 80 C. under 0.15 mm. Hg pressure.

Ortho- (diethoxymethyl) -phenyl-N-methyl-carbamate A solution of 138 parts of salicylaldehyde diethyl acetal, 46 parts of methylisocyanate and 0.5 part of triethylenediamine in 1,000 parts by volume of dry toluene was kept for 14 hours at room temperature. The resulting crystalline ortho-(diethoxymethyl)-phenyl-N-methyl-carbamate was filtered off, washed with 250 parts by volume of dry toluene and dried under vacuum. It melted at 92 to 93 C.

Ortho (dimethoxymethyl)-phenyl N methyl-carbamate, melting at 62 to 64 C. (after crystallization from dibutyl ether), was prepared in a similar manner, starting from salicylaldehyde dimethylacetal.

EXAMPLE 4 Ortho-( 1,3-oxathiolan-2-yl) -phenol 82 parts of Z-mercaptoethanol were mixed with 0.5

part by volume of concentrated hydrochloric acid and At 112 C. under a pressure of 0.05 mm. Hg, the ortho- (1,3-oxathiolan-2-yl)-phenol formed passed over and crystallized on standing. It melted at 72-74 C.

Ortho-( 1,3-oxathiolan-2-yl -phenyl-N- methyl-carbamate 15 parts of methylisocyanate and 0.1 part of triethylenediamine were added to a solution of 37 parts of ortho-(1,3-oxathiolan-2-yl)-phenol in parts by volume of dry toluene. The mixture was moderately cooled to maintain its temperature below 35 C. After a few hours, the resulting crystalline product was filtered oil and recrystallized from toluene or carbon tetrachloride. It melted at 108 to 109 C.

EXAMPLE 5 Ortho,para-dinitro-ortho'-( 1,3-dioxolan-2-yl -phenol A mixture of 196 parts of 3,5-dinitrosalicylaldehyde, 70 parts of glycol and 500 parts by volume of benzene was boiled in the presence of 1 part of anhydrous zinc chloride and 1 part by volume of concentrated phosphoric acid in a circulation distillation apparatus, until water was no longer being eliminated. After cooling, the product were filtered off and crystallized from chlorobenzene: it melted at 134 to C.

Ortho,para-dinitro-ortho'- 1,3-dioxolan-2-yl) -pheny1- N,N-dimethyl-carbamate 11.3 parts of dimethylcarbamic acid chloride were added to a mixture of 25.6 parts of ortho,para-dinitro- EXAMPLE 6 Dusting agent Equal parts of an active substance described in Examples 1 to 5 were mixed with precipitated silica and finely ground. When this powder is mixed with kaolin or talcum, it may be used in the form of dusting preparations having the desired concentration of active substance. In general, preparations containing 1 to 5% of active substance are preferred.

Spray powder To manufacture a spray powder, the following ingredients, for example, were mixed and then finely ground.

Parts Active substance of Examples 1 to 5 50 Hisil (highly adsorbent, precipitated silica) 20 Bolus alba (kaolin) 25 Reaction product from para-tertiary octylphenol and ethylene oxide r 3.5 Sodium 1 benzyl-Z-stearyl-benzimidazole-6,3'-disulphonate 1.5

Emulsion concentrate Readily soluble active substances were also formulated in the form of an emulsion concentrate as follows.

Parts Active substance 20 Xylene 70 Mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecyl benzenesulphonate were mixed. On dilution with Water to the desired concentrat1on, an emulsion suitable for spraying was obtained.

EXAMPLE 7 The active substance of Example 1 and the active substance carbaryl were subjected to a comparative test to establish their contact effect against houseflies and corn 'Weevils. The new substance displayed a much greater, distinct contact-insecticidal effect.

When applied in a concentration of 0.04% in the control of aphids (aphis fabae) on young bean plants, it was found that after 2 days the active substance of Example 1 had completely destroyed the aphids. It was found to have a good diffusion and distinct systemic effect.

Carbaryl was found to be ineffective in these tests. Carbaryl is the common name for l-naphthyl-N-methyl-carbamate.

The above-mentioned active substance is active in limited concentrations of 1.2 parts per million against aedes larvae (24 hours).

The compound was also tested in dust form against various pests (1%, 2 g./-m. kg. per hectare) and the following results were recorded:

Percent after- 6 hours 24 hours Phyllodronia germam'ca 100 Porcellic scaber 100 Formica rufa 100 10 Phosphoric acid ester I 6 Phosphoric acid ester II 13 in 7 per pest Phosphoric acid ester III 9 active substance of Example 1.

I =0,0-dimethyl-O- (3 -methyl-4-nitrophenyl -thionophosphate II =0,0'-dimethyl-O-( 1-chloro-l-N-diethyl-carbaminyll-prop en-2-yl phosphate III=0,0-dimethyl-O-(4-methylmercapto-3-methylphenyl -thionophosphate.

The active substance of Example 1 acts also against spider mites (Tetranychus urticae).

When tested as a stomach poison on Carausius, the said active substance displayed a good effect, against Prodenia a moderate to good effect and against Gastroidea rather a good effect.

EXAMPLE 8 Cont-act action against Musca: domestica The test was carried out in a Petri dish. 1 ml. of a 1000 ppm. acetonic solution of active ingredient to be tested is pipetted on each of the two halves. After evaporation of the solvent 10 immobilized flies (cooling of the test individuals in a test tube in crushed ice) were put on the bottom of the dish whereupon the lid was put on. Within a few minutes all the flies were back to normal. Control took place after one hour and the results are given below as the knockdown effect in percent.

Compound: Knockdown effect, percent Example 1 100 Example 2.1 100 Example 2.2 100 Example 4 EXAMPLE 9 Action against spider mites (Tetra'nychus urticae) 12 hours prior to the testing treatment dwarf bean plants (Phqseolus vulgaris) in the two-leave stage were infested with cultured mites. At the time of spraying the plants with an 800 p.p.m. emulsion of active ingredient by means of a chromatographic atomizer all possible living stages of mites were found on the plants. The evaluation was made after 2 and 7 days.

Killing in percent after- Compound 2 days 7 days Example:

EXAMPLE 10 Action against midges (Aedes aegypti) Compound: 3 hours, percent Example 1 100 Example 2.1 100 Example 2.2 100 Example 4 100 1 1 EXAMPLE 11 Action against bugs (Cimex lectularius) This test was carried out according to the statement in Example with the following exceptions: the acetonic solution (1 ml. of a 10 p.p.m. solution of active ingredient) was applied to filter paper which was placed on the bottom of a Petri dish of 9 cm. of diameter. Ten adult bugs were put on the paper and exposed for 48 hours to the action of the active ingredient. The test was repeated twice with the following results. killed bugs (twice 10 bugs) are indicated as 100%.

Killing effect after Compounds: 48 hours, percent Example 1 a- 9 Example 2.1 100 Example 2.2 100 EXAMPLE 12 Action against cockroaches (Periplarzeta americana and Blatta orientalis) A 5% dusting agent was prepared according to Example 6 using as carrier exclusively talcum. By mixing equal parts of dusting preparation and talcum a dilution series with progressive dilution was made in which every step contained half the quantity of active ingredient contained in the preceding step. Accordingly, the series thus made had a content of active ingredient of 5, 2.5, 1.2, 0.6, 0.3, 0.15, 0.08% which corresponds to an amount of 100, 50, 25, 12.5, 6.2, 3.1, 1.5 mg. of active ingredient per m9 when 2 g. of dusting preparation are applied. The test was carried out on green filter paper by means of a bell-shaped application apparatus and an amount of dusting preparation which corresponds to 2 g. per m. and was applied with compressed air. The test animals which were in the fifth larvae stage (L-S) were put on the treated paper surface. Evaluation took place 24 hours later and the results listed below indicate the minimum concentration necessary to provide a 100% killing effect within 24 hours.

Minimum concentration in mg. providing 100% killing within 24 hours of- Periplameta Blatta Compound americana orientalis Example:

What is claimed is: 1. O-phenylcarbamate compound of the formula:

12 4. A compound as claimed in claim 2 which is ortho- (4-ethyl-1,3-dioxolan-2-yl)phenyl-N-methylcarbamate.

5. A compound as claimed in claim 2 which is ortho- (4,5-dimethyl 1,3 dioxolan 2 yl)-phenyl-N-methylcarbamate.

6. A compound as claimed in claim 2 which is ortho- 1 ,3-oxathiolan-2-yl) phenyl-N-methylcarbamate.

7. An O-phenylcarbamate compound of the formula:

OCO-NHCH3 OCH:

O 0 Hz 8. An O-phenyl carbamate compound selected from the group consisting of ortho-(1,3-dioxolan-2-yl)-rneta'-methylphenyl-N- methyl-carbamate; ortho-( 1,3-dioxolan-2-y1) para-methylphenyl-N- methyl-carbamate; para-chloro-ortho-( 1,3 dioxolan-2-yl phenyl-N- methyl-carbamate; para-bromo-ortho-( 1,3-dioxolan-2-yl phenyl-N- methyl-carbamate; ortho-para-dibromo-ortho'- 1,3 -diox0lan-2-y1) phenyl- N-methyl-carbamate; ortho,para-dinitro-ortho-( 1,3-dioxo1an-2-yl phenyl- N-methyl-carbamate; and ortho,para-dinitro-ortho'-( 1, 3-dioxo1an-2-yl phenyl- N,N-dimethyl-carbamate. 9. An O-phenyl carbamate compound selected from the group consisting of ortho-(4-vinyl-1,3-dioxolan-2-yl)phenyl-N-methylcarbamate; ortho- (4-chloromethy1- l ,3 dioxolan-Z-yl phenyl-N- methyl-carbamate ortho-( 1,3-dioxan-2-yl)-pheny1-N-methyl-carbamate; ortho- (4-methyl- 1,3-dioxan-2-yl phenyl-N-methylcarbamate; ortho- (5,5-dimethyl- 1, 3-dioxan-2-yl phenyl-N-methylcarbamate; ortho- (4, 5,6-trimethyl-1,3-dioxan-2-yl)phenyl-N- methyl-carbamate; ortho-(S-methyl-S-nitro-1,3-dioxan-2-yl)-phenyl-N- methyl-carbamate; and ortho-1,3-dioxep-5en-2-yl-phenyl-N-methyl carbamate. 10. An O-phenyl carbamate compound selected from the group consisting of meta-( 1,3-dioxolan-2-yl) phenyl-N-methyl-carbamate;

and meta- 4,5 dimethyl- 1 ,3-dioxolan-2-yl phenyl-N- methyl-carbamate.

References Cited UNITED STATES PATENTS 3,349,115 10/1967 Weil et a1. 260479 3,317,561 5/1967 Levy et al 260327 3,193,561 7/1965 Addor 260327 HENRY R. JILES, Primary Examiner C. M. S. J AISLE, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent 3,181,301 I Dated Dec mber 25. 1973 Inventor(s) Erwin Nikles Volker Dittrich and Ladislaus Pinter 7 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 12, line 2 the portion of the chemical nam appearing as' ",4ethyl"o should read "4methyl" Claims 8 end 9 (column 12, lines 16 48) should be p i deleted. s v

Signed and sealed this l8thday of June (SEAL) Attes't:

EDWARD M.FLETC HER,JR. Attesti'ng Officer c MARSHA LL 1mm Commissioner of Patents F ORM PO-1050 (10-69) uscoMM-Dc seam-pas I UVS. GOVERNMENT PRINTING OFFICE: I969 O-366-334 

